Certain substituted phosphorus containing alkyl thio methyl carboxylates and their uses as insecticides and acaricides

ABSTRACT

X, R4 and R5 are as defined and R8 is alkyl C1 or C2 or halogen, aryl, haloaryl substituted derivatives thereof; or   X and R4 are as defined are used as insecticides and acaricides. Certain substituted phosphorus containing alkyl thio methyl carboxylates of the formula IN WHICH R1 is alkyl or alkoxy and R2 is alkyl, Q is: R3 is alkylene, C1-C4; X is sulfinyl or thio and R4 is alkyl, C1-C4; or   X and R4 are as defined and R5 is a trivalent saturated hydrocarbon, C1-C3; or   X, R4 and R5 are as defined and R6 and R7 are hydrogen, alkyl C1-C6, aryl, halo or cyano substituted alkyl or aryl, or tetrahydro furfuryl or when R6 and R7 are taken together, an alkylene, C2-C6, ethyleneoxyethylene or ethylenethioethylene groups; or   D R A W I N G

United States Patent Kezerian 51 Sept. 19, 1972 [54] CERTAIN SUBSTITUTED PHOSPHORUS CONTAINING ALKYL THIO METHYL CARBOXYLATES AND THEIR USES AS INSECTICIDES AND ACARICIDES [72] Inventor: Charles Kezerian, Orinda, Calif.

[73] Assignee: Stauffer Chemical Company, New

York,N.Y.

[22] Filed: Sept. 2, 1970 [21] Appl. No.: 69,095

Related US. Application Data [62] Division of Ser. No. 681,576, Nov. 8, 1967,

Pat. No. 3,562,362.

Primary Examiner-Albert T. Myers Assistant Examiner-Frederick E. Waddell Att0rneyWayne C. .laeschke and Edwin H. Baker 57 ABSTRACT Certain substituted phosphorus containing alkyl thio methyl carboxylates of the formula in which R is alkyl or alkoxy and R is alkyl, Q is:

in which R is alkylene, C ri; X is sulfinyl or thio and R is alkyl, C -C4; 0r

f -(L (..llzX 1h R:-

(H:---o--u1nxm in which X and R are as defined and R is a trivalent saturated hydrocarbon, C -C or in which X, R, and R are as defined and R and R are h dr en, alk lC -C ar 1 halo or c ano'substituted aficyl gr aryl, r te trahgldro turfuryl orivhen R and R are taken together, an alkylene, C -C ethyleneoxyethylene or ethylenethioethylene groups; or

in which X, R, and R are as defined and R is alkyl C, or C or halogen, aryl, haloaryl substituted derivatives thereof;

CI-I -OCHzXR4 JC(0)-O-CHzXRl CIIr-COCHXR4 in which X and R are as defined are used as insecticides and acaricides.

16 Claims, No Drawings in which R is selected from the group consisting of alkyl having from 1 to 4 carbon atoms, preferably from one to two carbon atoms; an alkoxy having from one to fourcarbon atoms, preferably from one to two carbon atoms, and most preferably ethoxy;

R is an alkyl group having from one to four carbon atoms, preferably from one to two carbon atoms, and most preferably ethyl; Q is selected from the group consisting of:

R is an alkylene group having from one to four carbon atoms, preferably from one to two carbon atoms,

X is selected from the group consisting of thio and sulfinyl, preferably thio,

R is an alkyl group having from one to four carbon atoms, preferably from one to two carbon atoms;

in which X and R are defined as above and R is a trivalent saturated hydrocarbon group having from one to three carbon atoms, preferably from one to two carbon atoms;

(C) (I) Ra in which X, R and R are defined as above and R and R are independently selected from the group consisting ofhydrogen; alkyl having from one to six carbon atoms and aryl, preferably phenyl, substituted derivatives thereof wherein the substituents are selected from the group consisting of halogen, preferably chloro, and cyano; and tetrahydrofurfuryl and when R, and R are taken together, a member selected from the group consisting of alkylene having from two to six carbon atoms, ethyleneoxyethylene, and ethylenethioethylene; and

wherein X, R, and R, are defined as above and R, is.

selected from the group consisting of alkyl having from i to 6 carbon atoms, and substituted derivatives therein in which said substituents are selected from the group consisting of halogen, preferably chlorine, aryl, preferably phenyl, and haloaryl, preferably chlorophenyl; and

in which X and R are defined as above.

The compounds of this invention can be prepared by various processes which are also features of this invention. In the following formulas R R R R R R R and R are as previously defined and K is an alkali metal and Hal is chloro or bromo radical, preferably chloro.

A. Compounds of the formula can be prepared in two steps according to the following general reaction:

R1 S H I! P-SK Hal-R;-C-OH Hal-CHzSRr Compound A Compound B Compound More specifically, in step 1, Compound A can be reacted with Compound B and then the intermediate reaction product, in step 2, can be reacted with Compound C. In the alternative, Compound B can be reacted with Compound C and the intermediate reaction product, in a second step, can be reacted with Compound A.

B. By another process, compounds of the formula in which R is alkylene radical having from two to three carbon atoms can be prepared in two steps by the following general reaction:

R1 H E. Compound of the formula PSH (l:=c-p ou Hal-CHzS R4 R 6 R20 n b RI q g Compound E Compound D Compound C \il R/ V c. H Us W. V .rdi. W V V V s 5 in which R,, and R are selected from the group consist- 0 ms ing of methyl provided that both R, and R can not be ll methyl. More specifically, in step 1, Compound E can be reacted with Compound D and the intermediate can be prepared by the processes described in part (C) reaction product can be reacted, in step 2, with Com- 1 with the exception that a compound of the formula pound C. In the alternative, Compound C can be reacted with Compound D and then the intermediate 31 reaction product, in a second step, reacted with Compound E. 1-mi1n it? C. Compound of the formula o \fi O CIS R Compound III P s is substituted for Compound D or by the-processes 12,0 CO-CH SR described in part (D) with the exception that a com- I pound of the formula can be prepared in two steps according to the following H 0 R, general equation: 2 1 iN 0 ll R1 R! i (L0H nukemsni (ll-(F011 P-SK Hal-BK 0 m0 0-011 Hal-CH,S R4 (fmpou'ld I u is substituted for Compound G. Compound H and I can 90290,}? A I qompmmd F Compound 0 be prepared by well known procedures, for example, by

reacting a compound of the formula More specifically, the above reactions can be carried 0 0 out by reacting Compound A with Compound F, in step I; 1, and then reacting, in step 2, 1 mole of the intermediate reaction product thereof with 2 moles of Compound C. In the alternative, 1 mole of Compound F can be reacted with 2 moles of Compound C and then, as a d n, 0 second step, the intermediate reaction product thereof 40 can be reacted with Compound respectively, with an nnnne of the formula.

D. Alternatively, compounds of the formula N-u H 11 fi (F) Compound of the formula P-s-R,\ O R10 goemsm R; s {Lo-1n O l Ht R o c-oou SR in which R is a trivalent saturated hydrocarbon group 2 2 4 having from two to three carbon atoms, can be Prepared m steps accordmg to the fonowmg can be prepared by the processes described in part (0) general equation: with the exception that a compound of the formula H o I? Rt s 1| 0-0-12:

\1! CCOH /P-SII 914F011 2(Ha1-ClhSR4) Hal-Rt R20 J C-OH Compound E Compound G Compound C 0 Compound I in whlch of Compound 0 IS selected from the group is substituted for Compound I) or they can be prepared consisting ofhyqrogen and y by the processes described in Part (1)) with the excep- Aecordingly, In Step 1 Compound E can be reacted tion that a compound of the formula.

with Compound G and then 1 mole of the intermediate 0 compound formed thereby can be reacted with 2 moles g ll of Compound C, in a second step. in the alternative, 2 I5 moles of Compound C can be reacted with Compound 1g 3 G in a first step and the reaction product thereof can be I c 7 reacted with Compound E. Compound h is substituted for Compound (1. Compounds .1 and K mm bu prepared by well known procedures by reacting a compound of the formula respectively, with an alcohol of the formula It OlI 1 1) Compounds of the formula mm Inprepared in two stops according to the followinc; general equation:

reaction product produced thereby reacted with Compound A.

All the reactions set out above between Compound C with a compound or intermediate reaction product containing one or more carboxylic acid moieties are preferably carried out in a solvent and in the presence of an HCl or l-lBr acid acceptor which are well known in the art. The reaction can proceed without heating or the reactions are exothermic, however, heating between about 50 to 80 C. is preferable as such 4 reduces the reaction time.

In those reactions in which Compound A or Compound E is a reactant the reaction proceeds readily with heating between about 50 C. and 80 C. in a solvent.

All of the reactions set out above should be carried out under anhydrous conditions. Examples of solvents are acetone, ether, halogenated hydrocarbons such as carbon tetrachloride, or a liquid aliphatic or aromatic hydrocarbon, such as hexane, benzene, xylenes or the 5 like. The addition reactions to unsaturated compounds in some cases proceed vigorously, usually after an induction period of a few minutes. These addition reactions are preferably effected initially at below about 40 C., with the reaction mixture eventually being heated at 6 about 60 C. for several hours to insure completion of the reaction. Reactions involving evolution of a hydrogen chloride or hydrogen bromide are, preferably effected in the presence of a hydrogen chloride or hydrogen bromide acceptor, such as an organic tertiary nitrogen base such as pyridine or preferably triethylamine or K CO Bases which form a salt and water with the hydrogen chloride or bromide should not be used as water has a deleterous effect on the reactions.

When the reactions are complete, any precipitate formed can be filtered off and any solvent or other volatile material removed by distillation.

The compounds of subdivision A through F of the preceeding processes can be converted to their sulfinyl derivatives by reacting them with an oxidizing agent such as hydrogen peroxide preferably in the presence of a solvent such as glacial acetic acid. This reaction can be carried on conveniently at room temperature with cooling. Thus as a result of this conversion, the moiety -CH SR of these compounds is oxidized to the The compounds of this invention can be prepared in accordance with the teaching of the following illustrative examples:

EXAMPLE I Methylthiomethyl, 2-(0,0 diethyl phosphosdithio) 1 -methyl propionate.

021150 s on. o

i scH2oH -o-omscm 41.3 g. (0.135 M) of B(0,0

diethylphosphorodithio) 1 methyl propionic acid and 150 ml. acetone was treated with 13.5 g. (0.14 M) monochlorodimethyl sulfide. While stirring at 20C., 13.6 g. (0.135 M) triethylamine was added and the mixture stirred for 30 minutes, then refluxed 30 minutes. Benzene 200 ml. was added with sufficient water to separate the organic layer. This was washed with 5% HaHCO then water, dried over anhydrous magnesium sulfate, then distilled under vacus to remove solvent and volatile. There was obtained 3l.g. of yellow oil with an N, of 1.5160 and Infra red spectra corresponds to the above structure.

EXAMPLE ll Bis methylthiomethyl, a (0,0 diethylphosphorodithio) 11.8 g. (0.05 M.) of his methylthiomethyl maleate and 12 g. (0.065 M) 0,0 diethylphosphoro dithioic acid and a trace of hydroquinone were heated to C. for 16 hours. The mixture was diluted with ml benzene and washed with 5% Hal-[CO solution, then with water. The organic layer was dried over anhydrous magnesium sulfate, then distilled under vacuo to remove solvent and volatiles. There was obtained 17 ture. Calc. For C, H O PS C34.2, H 5.46, P 7.32; Found C 33.71, H 5.74, P 8.62.

EXAMPLE lll N,N dimethyl, methylthiomethyl,a(0,0' diethylphosphorodithio) succinanate.

Cal-I50 33 g. (0.1 mole) of N N dimethyla(0,0' diethylphosphoro dithio) succinamic acid and 13.9 g. (0.1 mole) K CO were added to 100 ml. acetone. Monochlorodimethyl sulfide 9.6 g. (0.1 mole) was added, and the mixture stirred overnight, and finally refluxed for 2 hours, Benzene 200 ml. was added with sufficient water to separate the organic layer. This was washed with water, NaOl-I, again with water, then dried over anhydrous M,,SO and distilled under vacuo (below 45 C.) to remove solvent and volatiles. There was obtained 30 g. of a tan oil N l.5250. Infra red corresponds to the above structure. Calc for C I-1 NO PS C 37.0; H 6.22; P 7.96; N 3.6; S 24.65 Found C 38.61; H 6.59; P 8.1 1; N 3.12; S 25.41.

EXAMPLES lV succinamate.

30 g. (0.08 mole) N,N dimethyl, methylthiomethyl, a (0,0 diethylphosphorodithio) succinamate in 100 ml. glacial acetic acid was treated dropwise over 1 hour with 9 ml. (0.08 mole) 30% H 0 keeping at room temperature with cooling. Stir overnight at room temperature. Benzene 300 ml. and water 500 ml. were added. Separate the organic layer and wash with water till the washings are neutral, then dried over anhydrous Mg.SO., filtered and distilled under vacuum to remove solvent and volatile. A low yield 12 g. of yellow oil was obtained N 1.5248. Infra red corresponds to the above structure, with a strong sulfoxide bond at 10.90 cm".

EXAMPLE V Ethyl, methylthiomethyl,a(0,0 dimethylphosphorodithio) succinate.

(11 o umsuu,

13 g. (0.063 M) of ethyl, methylthiomethyl maleate and 11 g. (0.07 M) of 0,0'dimethylphosphorodithioic acid were mixed with ml. benzene and stored for 2 days. The mixture was washed with 5% HaHCO solution, then with water. The organic solution was dried over anhydrous magnesium sulfate and distilled under vacus to remove solvent and volitiles. There was obtained 12.5 g. of a yellow oil, with an N of 1.5169. Infra red spectra corresponds to the above structure. Calc. for C H O PS P 8.55, S 26.5; Found P 8.24 S 26.77.

Table I through Table V contains other compounds of this invention that can be prepared by the procedures described in Examples l-V.

TABLE I \II II PSR3COCHzXR4 Compound number R; R; R; X R; no

1. Ethoxy. Ethyl. CH S Methyl. 1. 5214 2 "d0 .(10 CH3CH1- S dO.. 1.5212

3 ..do ..do.. (3H3 S ...do 1.5140

-CHCH 4a ..do ..do.. (3H3 S ..-do..--. 1.5160

CI IZCII 0 5. .......(lo .......(lo.- (7113 Q1 ...do.. 1.5260

-on,ou

TABLE II (I? R1 S COCH1XR4 P-S-Rs R 0 (fi-O-OHzXR;

Compound number R R R5 X R4 mm 61) Ethoxy... Ethyl... (|3H S MethyL. 1.5344

7 Methoxy.. MethyL. ([]H S ..-do..--. 1. 5580 TABLE Ill ii R1 S C-N l Slt5 R1 11 0 Table Ill-(unlinucd Compound number R R: R; X R4 R11 R1 1111" 80 Ethoxy... Ethyl." CH: S Met-hylnn Methyl Methyl 1. 5250 1111 do .do.. CH2- 0 do do do 1524s CH S 10 do ..-.-..do.. CH1- S '.-.do n-Buty n-Buty 1.5110

11..:. do do. CHz- 5) ..do .......do.... do 1.5120

5 CHZ-CH2 12 do ..do.. cms -..do I 1.53%

- cm-cm 13 do do CH1 0 do CHz-CH: 1.5346

-OH g OH: I

\CHPCH2 14 do do CH2- S do Methyl Phenyl 1.5518

16 do ..do. CH1- 0 do do do 1.5509

CH ST 16 .d0.- dO CHz- S do CHz-CH: 1.5343

CH -CH/ 17 do do CHz- S do Hydrogen t-Butyl 1.5164

18 do ..do. CHz- 0 do CHr-CH: 1.5322

-( JH- SI 0 CHPCHg 19 do do CH; S do 0 1.5271

CH CH CH CH;

Hz H3 20 do "do..." CIIz- O d o 2 -CH S CHC61 CH:

CH: Hg

21 do ..do. CH1 S do CHzCHr-CzHqOCH; CH1CH1CH10CH; 1.5126

22 do .do CH1 S .do Cyclohexyl Cyanoethyl 1.5269

( lI-I t 23 do do.... CH2 S do Cyanoothyl do 1.5318

24 do ..do CHz 0 do Cyclohexyl do 1.5251) TABLE IV 0 R S 3-0--R LMK R20 COCH;XR4

Compound number R1 R2 R5 X Ra Ru "1:

260 Methoxy. MethyL. CI-I S Methyl" Ethyl Ethoxy Etl1yl CH5 s Mao do 1.5120

27 do .do CHz- 0 ..do do 1.5195

28 do do.... CH: S -..do -CH2CH2CL 1.5213

29 do .d0 CH; S .do Phony] 1.5409

I l2 7 TABLE IV-(uminucd Com ound num er R1 R2 R5 X B4 Rs up a0 do ..do. :m g .do do 1. 5456 31 do ..do..... ([3112- S do.. d-chlorophenyl... 1. 6486 32 do do. on:- L .do ..do 1. 5511 cns TABLE v given in Table ll under the column BA. R 0 Acaricidal Evaluation Test. The two-spotted E mite(2SM), Tetranychus telarious (Linn.), was eml (o) o cmxm played in tests for miticides. Young pinto bean plants in R I v the primary leaf stage were used as the host plants. The

cm-o-o -oman.

young pinto bean plants were Infested with several hun- 20 dred mites. Dispersions of candidate materials were ggg fi R, R2 X R prepared by dissolving 0.1 gram in 10 ml. of a suitable as Emoxy EVUWLW S Methyl solvent, usually acetone. Aliquots of the toxicant solua-Prepared in Example I. b--Prepared in Example II.

c-Prepared in Example III.

d-Prepared in Example IV. e-Irepared in Example V.

As previously stated the compounds of this invention are useful as insecticides, especially systemic type insecticides.

Insecticidal Evaluation Test. The housefly (HF) Musca domestica (Linn.) was subjected to evaluation tests for insecticides incorporating the compounds of the present invention.

TwentyJive female flies, 3 to 5 days old, were caged in cardboard mailing tubes 3-96 inch in diameter 2-56 inch tall. The cages were supplied with cellophane bottoms and coarse mesh nylon tops. Each cage was provided with food and water. The candidate toxicant was dissolved in a volatile solvent, preferably acetone. The solution was pipetted into ,a Petri dish bottom, allowed to air dry and placed in a cardboard mailing tube cage. The flies' were continuously exposed to the known residue of the active compound in the cage. After '24 and 48 hours, counts were made to determine living and dead insects. The LD-SO values were calculated using well known procedures. The results of this insecticidal evaluation test is given in Table II under HF. The Lygus bug (LB) Lygus hesperus was treated similarly as the houseflies, except 10 to insects well used per cage. The caged insects were sprayed with the candidate compounds at various concentrations. After 24 and 72 hours, counts were made to determine living and dead insects. The LD-SO (percent) values were calculated. These values are reported under the column LB in Table I].

The insect species bean aphid (BA) Aphis fabae was also employed in the test for insecticidal activity. Young nasturtium plants were used as the host plants for the bean aphid. The host plant was infested with approximately 50 of the aphids. The test chemical was dissolved in acetone, added to water which contained a small amount of Sponto 221, an emulsifying agent. The solution was applied as a spray to the infested plants. Concentrations ranged from 0.05 percent downward until an LD value was achieved. These results are tions were suspended in water containing 0.01 v/v Sponto 221, polyoxy-ethylene ether sorbitan monolaurate, an emulsifying agent, the amount of water being sufficient to give concentrations of active ingredient ranging from 0.25 to 0.0008 percent. The test suspensions were then sprayed on the infested pinto bean plants. After 7 days, mortalities of post-embryonic and ovicidal forms were determined. The percentage of kill was determined by comparison with control plants which had not been sprayed with the candidate compounds. The LD-50 value was calculated using wellknown procedures. These values are reported under the columns ZSM-PE and ZSM-Eggs in Table VI.

Systemic Evaluation Test. This test evaluates the root absorption and upward translocation of the candidate systemic compound. The two-spotted mite (28M), Tetracyshus relarious (Linn.) and the bean aphid (BA), Aphisfabae, were employed in the test for systemic activity. a

Young pinto bean plants in the primary. leaf stage were used as host plants for the two-spotted mite. The pinto bean plants were placed in bottles containing 200 ml. of the test solution and held in place with cotton plugs. Only the roots were immersed. The test solutions were prepared by dissolving the compounds to be tested in a suitablesolvent, usually acetone, and then diluting with distilled water. The final acetone concentration never exceeded about 1 percent. The toxicants were initially tested at a concentration of 10 parts per million (ppm) Immediately after the host plant was placed in the test solution it was infested with the test species. Mortalities were determined after 7 days.

Young nasturtium plants were used as the host plants for the bean aphid. The host plants were transplanted into one pound of soil that had been treated with the candidate compound. Immediately after planting in the treated soil the plants were infested with the aphids. Concentrations of toxicant in the soil ranged from 10 p.p.m. per pound of soil downward until an LD-SO value was obtained. Mortality was recorded after 72 hours.

The percentage of kill of each test species was determined by comparison with control plants placed in ported in Table VI under the columns BA-sym and ZSM-sym.

these agents commonly comprises 1-15 percent by weight of the pesticidal compositions although the proportion is not critical and may be varied to suit any particular situation.

I claim: TABLE VI 1. The method of killing acarids comprising applying I thereto an acaricidally effective amount of a compound Compound 111- 1.1; BA BA-sym 2 SM Ofthe mula Number g p.p.m. PE Eggs Sym. ppm

1 30 .008 .003 1 .003 .03 0.5 2 80 .008 .030 3 .008 0.5 R S 3 30 .005 .008 0.8 .001 .008 0.3 4 30 .030 .030 3 .001 .005 3 P-S-Q 5 10 .005 .050 3 .001 .01 1 6 10 .001 .003 0.3 .001 .008 0.1 R20 7 30 .003 0.8 .0003 .03 0.3 8 .005 .0005 0.8 .003 .003 0.5 9 15 .010 .003 3 .003 .003 0.5 10 so .030 .008 3 .005 .030 0.8 whfch 1 A 53 28 10 133 .838 R 1s selected from the group consisting of alkyl hav- 13 I050 l 603 mg from 1 to 4 carbon atoms and alkoxy having 14 30 .008 .005 3 .001 .030 0.8 20 from one to four carbon a m 15 50 .050 .008 1 .005 .030 1 R i an lk l mu havin l6 30 .008 .003 0.8 .003 .008 0.8 m y g p gfrom one to four carbon 17 30 .300 .003 1 .005 .030 0.8 0 18 8 .008 .003 0.8 .001 .008 0.5 0 1s a radlcal selected from the group cons1st1ng of: 19 50 .030 .003 3 .003 .003 1 20 30 .010 .003 3 .003 .003 0.8 21 50 .010 .005 0.8 .003 .008 0.8 2 22 80 .030 3 .003 .008 1 23 30 r .003 0.3 3 r s (A) C 0 24 30 r .005 3 .003 .30 0.8 2s 50 .003 .008 3 .005 .03 3 Whlch 26 20 003 3 .005 1108 R is an alk lene rou havin from one f 27 30 .030 .003 3 .005 '.030 3 g p g to our car 28 20 .010 .003 0.8 .005 .008 0.4 30 1 29 30 .050 .008 1 .003 .008 0.8 X 18 selected from the group consrstmg of th1o and 30 30 .010 .008 1 .003 .008 0.8 lfi l; and 31 50 .050 .008 3 .003 .008 0.8 32 30 030 008 3 D03 D08 M R 1s an alkyl group having from one to four carbon atoms; 35 (B) 0 Not tested. g R

-R As those in the art are well aware, var1ous technlques are available for incorporating the active component or 40 f toxicant in suitable pesticida] compositions. Thus, 0 pesticidal compositions can be conveniently prepared in which in the form of liquids or solids, the latter preferably as X and R are defined as above and homogeneous free-flowmg dusts commonly formulated R is a trivalent saturated h drocarbon rou havin by admixing the active component with finely divided sfrom one to three carbon items. g p g solids or carriers as exemplified by talc, natural clasy, diatomaceous earth, various flours such as walnut shell, 0 0 R, wheat, soya bean, cottonseed and so forth.

Liquid compositions are also useful and normally comprise a dispersion of the toxicant in a liquid media, 7 although it may be convenient to dissolve the toxicant C O CHXR directly in a solvent such as kerosene, fuel oil, xylene, alkylated naphthalenes or the like and use such organic in which X R4 and R5 are defined as above and R6 and solunons fhrectly' w the more R are independently selected from the group consistprocedure1sto employ d1spers1ons of the toxlcant 1n an ing of hydrogen; alkyl having from one to six carbon aqueous media 3 such composltlons, may be atoms and phenyl, and substituted derivatives thereof f by fonflmg a concefmrated 501mm of the wherein the substituent is selected from the group con toxicant 1n 8 sultable g f solveflt followed by sisting of chloro and cyano; and tetrahydrofurfuryl; d1spers1on m water, usually with the a1d of surface active agents. The latter, which'may be the anionic, ca- 0 f tionic or nonionic types, are exemplified by sodium o stearate, potassium oleate and other alkaline metal soaps and detergents such as sodium lauryl sulfate, OCH XR sodium naphthlene sulfonate, sodium alkyl z 4 naphthlanee sulfonate, methyl cellulose, fatty alcohol ethers, polyglycol fatty acid esters and other polyoxyethylene surface active agents. The proportion of wherein X, R, and R are defined as above and R is selected from the group consisting of alkyl having from in which X and R are as defined.

2. The method of claim 1 in which Q of said compound is the radical of subdivision (A).

3. The method of claim 1 in which Q of said compound is the radical of subdivision (B).

4. The method of claim 1 in which Q of said compound is the radical of subdivision (C).

5. The method of claim 1 in which 0, of said compound is the radical of subdivision (D).

6. The method of claim 1 in which Q of said compound is the radical of subdivision (E).

7. The method of claim 3 in which R is ethoxy, R is ethyl, R is methyl, X is thio and R is H C Ht- H 8. The method of claim 3 in which R, is methoxy, R is methyl, R is methyl, X is thio and R is I HC- H 9. The method of killing insects comprising applying thereto an insecticidally effective amount of a compound of the formula II (A) Rsco-omxni in which R, is an alkylene group having from one to four carbon atoms;

X is selected from the group consisting of thio and sulfinyl; and

R is an alkyl group having from one to four carbon X and R are defined as above and R is a trivalent saturated hydrocarbon group having from one to three carbon atoms;

wherein X, R and R are defined as above and R is selected from the group consisting of alkyl having from one to six carbon atoms and substituted derivatives thereof in which said substituents are selected from the group consisting of chlorine, phenyl and chlorophenyl; and

in which X and R are as defined.

10. The method of claim 9 in which 0 of said compound is the radical of subdivision (A).

11. The method of claim 9 in which 0- of said compound is the radical of subdivision (B).

12. The method of claim 9 in which 0 of said compound is the radical of subdivision (C). so 13. The method of claim 9 in which Q of said compound is the radical of subdivision (D).

14. The method of claim 9 in which Q of said compound is the radical of subdivision (E).

15. The method of claim 11 in which R is ethoxy, R is ethyl, R is methyl, X is thio and R 16. The method of claim 11 in which R, is methoxy, R is methyl, R is methyl, X is thio and R is 

2. The method of claim 1 in which Q of said compound is the radical of subdivision (A).
 3. The method of claim 1 in which Q of said compound is the radical of subdivision (B).
 4. The method of claim 1 in which Q of said compound is the radical of subdivision (C).
 5. The method of claim 1 in which Q, of said compound is the radical of subdivision (D).
 6. The method of claim 1 in which Q of said compound is the radical of subdivision (E).
 7. The method of claim 3 in which R1 is ethoxy, R2 is ethyl, R4 is methyl, X is thio and R5 is
 8. The method of claim 3 in which R1 is methoxy, R3 is methyl, R4 is methyl, X is thio and R5 is
 9. The method of killing insects comprising applying thereto an insecticidally effective amount of a compound of the formula in which R1 is selected from the group consisting of alkyl having from 1 to 4 cArbon atoms and alkoxy having from one to four carbon atoms; R2 is an alkyl group having from one to four carbon atoms; Q is a radical selected from the group consisting of: in which R3 is an alkylene group having from one to four carbon atoms; X is selected from the group consisting of thio and sulfinyl; and R4 is an alkyl group having from one to four carbon atoms;
 10. The method of claim 9 in which Q of said compound is the radical of subdivision (A).
 11. The method of claim 9 in which Q of said compound is the radical of subdivision (B).
 12. The method of claim 9 in which Q of said compound is the radical of subdivision (C).
 13. The method of claim 9 in which Q of said compound is the radical of subdivision (D).
 14. The method of claim 9 in which Q of said compound is the radical of subdivision (E).
 15. The method of claim 11 in which R1 is ethoxy, R2 is ethyl, R4 is methyl, X is thio and R5 is
 16. The method of claim 11 in which R1 is methoxy, R2 is methyl, R4 is methyl, X is thio and R5 is 